Pyridine compouds which have useful insecticidal activity

ABSTRACT

An insecticidal compound of the formula ##STR1## wherein A completes a 5 or 6 membered aromatic ring selected from the group pyridyl, pyridyl substituted with C 1-5  alkyl, C 1-5  haloalkyl, C 1-5  alkoxy, C 1-5  alkylthio, C 1-5  alkylsulfonyl, cyano, halogen, phenoxy or C 1-5  dialkylamino, pyrazinyl, pyrazinyl substituted with C 1-5  alkyl or halogen, pyrazolyl substitited with C 1-5  alkyl, pyridazyl substituted with halogen, or thiazolyl substituted with halogen or C 1-5  alkyl; 
     R 1  is hydrogen or C 1-5  alkyl, C 1-5  haloalkyl, C 1-5  alkoxy, C 1-5  alkylthio, C 1-5  alkylsulfonyl, cyano, halogen, phenoxy, or C 1-5  dialkylamino; 
     X is substituted or unsubstituted C 1-3  alkylene or C 1-3  alkylidene; 
     R 2  is hydrogen, monoalkylcarbamoyl, C 1-5  dialkylcarbamoyl, C 1-5  alkoyl, C 1-5  alkyl substituted with halogen, C 1-5  alkoxy, C 1-5  alkylthio, C 1-5  alkoxycarbonyl, cyano, aryl, haloaryl, C 1-5  alkoxyaryl, furyl, thienyl, pyridyl, halopyridyl, thiazolyl or halothiazolyl, C 2-5  alkyenyl, C 2-5  alkynyl, C 3-6  cycloalkyl, aryl, or the radical 
     
         --Y--R.sub.5 
    
     and an insecticidal acceptable salt thereof.

This is a continuation of application Ser. No. 07/700,165 filed on Jul.9, 1991 now U.S. Pat. No. 5,304,566.

DESCRIPTION OF RELATED ART

The present invention relates to new amine derivatives, the processesfor the production thereof and insecticides containing the saidderivatives as effective compounds.

BACKGROUND ART

A large number of chemicals, for example, organophosphorus compoundssuch as parathion and malathion and carbamate compounds such as carbaryland methomyl, have been developed and put to practical use asinsecticides over many years. These insecticides have played a verygreat role for the improvement of agricultural production. However, inrecent years some of these insecticides are regulated on their usebecause of problems such as environmental pollution due to residue oraccumulation, or cause infestation of resistant insect pests as a resultof long-term use. Therefore, there is a need to develop new chemicalswhich have excellent insecticidal characteristics over various types ofinsect pests including these resistant insect pests and which can beused safely.

The following compound is known as the isomer compound of thisinvention, which has no insecticidal activity.

    TABLE 1      - Structure Formula      ##STR2##                                                                              C     ompound No. R.sub.1 X R.sub.2 R.sub.3 Z R.sub.4 Physical Properties [ ]     m.p. °C.      1     ##STR3##      H H N CN [123-126]      2 " " CH.sub.3 " " [141-143]       3 " " CH.sub.2      Cl " " [124-126]                                          4 " "     CH.sub.2      F " " [151-152]                                                   5 " "     CF.sub.3 " " [112-114]       6 " " C.sub.2      H.sub.5 " " [120-122]                                      7 " "     C.sub.3 H.sub.7      (n) " " [100-101]      8 " "     ##STR4##      " " [193.5-195]                       9 " " C.sub.4 H.sub.9      (t) " "                            10 " " CH.sub.2 OCH.sub.3 " "     [128-128.5]       11 " " CH.sub.2      SCH.sub.3 " " [116-118]      12     ##STR5##      " CH.sub.2 COOC.sub.2 H.sub.5 N CN n.sub.D      .sup.25.5 1.5608                                                 13 " " CH.sub.2 CH.sub.2     COOC.sub.2      H.sub.5 " "                                                     14 " "     CH.sub.2      NHCH.sub.3 " "                                                    15 "     " CH.sub.2      N(CH.sub.3).sub.2 " "                                           16 " "     CH.sub.2 CH.sub.2 CH.sub.2      Cl " " [114-115]      17 " "     ##STR6##      " " [190-191]      18 " " CH.sub.2      CN " " [106-108]                                          19 " "     CH.sub.2 CH.sub.2      CN " "      20 " "     ##STR7##      " " [187-189]      21 " CH.sub.3 H " " n.sub.D      .sup.25 1.5918                                22 " " CH.sub.3 " "     [101-103]      23 " " " " " [161-162]           HCl salt       24 " " CH.sub.2 Cl " " n.sub.D      .sup.26.5 1.5921                          25 " " CH.sub.2 F " " [79-80]      26 " " CF.sub.3 " " *1      27     ##STR8##      CH.sub.3 C.sub.2 H.sub.5 N CN n.sub.D      .sup.27 1.5742                                            28 " " C.sub.3 H.sub.7 (n) " "     [97-100]      29 " "     ##STR9##      " " n.sub.D      .sup.24.5 1.5829                  30 " " C.sub.4 H.sub.9      (t) " "                                31 " " CH.sub.2 OCH.sub.3 " "     n.sub.D      .sup.24 1.5803                                                     32 "     " CH.sub.2 SCH.sub.3 " " n.sub.D      .sup.24.5 1.6070                          33 " " CH.sub.2 COOC.sub.2     H.sub.5 " " n.sub.D      .sup.25.5 1.5604                                       34 " " CH.sub.2     CH.sub.2 COOC.sub.2 H.sub.5 " " n.sub.D      .sup.24.5 1.5605                   35 " " CH.sub.2 NHCH.sub.3 " "     n.sub.D      .sup.25 1.5861                                                     36 "     " CH.sub.2 N(CH.sub.3).sub.2 " " n.sub.D      .sup.25 1.5577                    37 " " CH.sub.2 CH.sub.2 Cl " "             38 " " CH.sub.2 CH.sub.2 CH.sub.2 Cl " " n.sub.D .sup.25.5     1.5830      39 " "     ##STR10##      " "      40 " "     ##STR11##      " "      41 " "     ##STR12##      " " n.sub.D      .sup.25.5 1.6040      42     ##STR13##      CH.sub.3 CHCH.sub.2       N CN                          43 " " CH.sub.2 CN " " n.sub.D .sup.25 1.5913             44 " " CH.sub.2 CH.sub.2      CN " " [112-114]      45 " "     ##STR14##      " "      46 " "     ##STR15##      " " [224-226]      47 " CHF.sub.2 H " "       48 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.5423                             49 " " C.sub.2 H.sub.5 " "       50 " C.sub.2      H.sub.5 H " " [101-103]                                     51 " "     CH.sub.3 " " [100-101]       52 " " C.sub.2      H.sub.5 " "                                               53 " C.sub.3     H.sub.7      (i) H " " [205-207]                                                54 "     " CH.sub.3 " "       55 " " C.sub.2      H.sub.5 " "      56 "     ##STR16##      H " "      57     ##STR17##      ##STR18##      CH.sub.3 N CN n.sub.D      .sup.25 1.5825                            58 " " C.sub.2      H.sub.5 " "                          59 " CH.sub.2 OCH.sub.3 H " "            60 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5711                        61 " CH.sub.2 SCH.sub.3 H " "         62 " " CH.sub.3 " " n.sub.D      .sup.25 1.5828                             63 " CH.sub.2 COOC.sub.2     H.sub.5 H " "       64 " " CH.sub.3 " " n.sub.D      .sup.25 1.5475      65 "     ##STR19##      H " "      66 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5928      67 "     ##STR20##      H " "      68 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6155      69 "     ##STR21##      H " "      70 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.6093      71 "     ##STR22##      H " "      72     ##STR23##      ##STR24##      CH.sub.3 N CN [112-114]      73 " CH.sub.2 CHCH.sub.2  H " " n.sub.D      .sup.25 1.5841                    74 " " CH.sub.3 " " n.sub.D .sup.25     1.5809       75 " CH.sub.2      CCH H " "                                                  76 " "     CH.sub.3 " " n.sub.D      .sup.25.5 1.5730                                      77 " CH.sub.2 CN     H " "      78 " " CH.sub.3 " " [127-128]      79 "     ##STR25##      H " "      80 " " CH.sub.3 " " [124-127]      81 "     ##STR26##      H " "      82 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.6045      83 "     ##STR27##      H " "      84 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6092      85 "     ##STR28##      H " "      86     ##STR29##      ##STR30##      CH.sub.3 N CN n.sub.D      .sup.25.5 1.5910      87 "     ##STR31##      H " "      88 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6162      89 "     ##STR32##      H " "      90 " " CH.sub.3 " " [115-117]      91 " OCH.sub.3 H " "      92 " " CH.sub.3 " " [110-112]      93 " CHO H " "      94 " " CH.sub.3 " "       95 " COCH.sub.3 H " " n.sub.D      .sup.25.5 1.5475                           96 " " CH.sub.3 " " [84-86]        97 " SO.sub.2      CH.sub.3 H " " [160-163]                                  98 " "     CH.sub.3 " "      99 "     ##STR33##      H " "     100 " " CH.sub.3 " " [112-114]     101      ##STR34##      COOC.sub.2      H.sub.5 H N CN                102 " " CH.sub.3 " " n.sub.D      .sup.25 1.5540                    103 " CONH.sub.2 H " "      104 " " CH.sub.3 " "     105 "      ##STR35##      H " "     106 " " CH.sub.3 " " [89-91]      107 " CONHCH.sub.3 H " "      108 " " CH.sub.3 " "      109 " CSNHCH.sub.3 H " "      110 " " CH.sub.3 " "     111      ##STR36##      H CH.sub.3 " "     112 " CH.sub.3 " " "     113      ##STR37##      H " " "     114 " CH.sub.3 " " "     115      ##STR38##      H " " " [83-85]     116      ##STR39##      CH.sub.3 CH.sub.3 N CN [76-78]     117      ##STR40##      H " " "     118 " CH.sub.3 " " " [145-147]     119      ##STR41##      H " " "     120 " CH.sub.3 " " " n.sub.D      .sup.25 1.5202                                 121      ##STR42##      H " " "     122 " CH.sub.3 " " "     123      ##STR43##      H " " "     124 " CH.sub.3 " " " n.sub.D      .sup.25.5 1.5580                                 125      ##STR44##      H " " "     126 " CH.sub.3 " " "     127      ##STR45##      H " " "     128 " CH.sub.3 " " "     129      ##STR46##      H " " " [162-163]     130 " CH.sub.3 " " " [105-107]     131      ##STR47##      H CH.sub.3 N CN     132 " CH.sub.3 " " " [138-139]     133      ##STR48##      H " " "     134 " CH.sub.3 " " " n.sub.D      .sup.25 1.5841                                 135      ##STR49##      H " " "     136 " CH.sub.3 " " " [107-109]     137      ##STR50##      H " " "     138 " CH.sub.3 " " "     139      ##STR51##      H " " "     140 " CH.sub.3 " " "     141      ##STR52##      H " " "     142 " CH.sub.3 " " "     143      ##STR53##      H " " " [122-124]     144 " CH.sub.3 " " " [110-113]     145      ##STR54##      H CH.sub.3 N CN [66-68]     146 " CH.sub.3 " " " n.sub.D      .sup.24.5 1.5790                                 147      ##STR55##      H " " "     148 " CH.sub.3 " " " [94-96]     149      ##STR56##      H " " " [130-132]     150 " CH.sub.3 " " " n.sub.D      .sup.25 1.5612                                 151      ##STR57##      H " " " [96-99]     152 " CH.sub.3 " " " n.sub.D      .sup.25.5 1.5800                                 153      ##STR58##      H " " "     154 " CH.sub.3 " " "     155      ##STR59##      H " " "     156      ##STR60##      CH.sub.3 CH.sub.3 N CN     157      ##STR61##      H " " "     158 " CH.sub.3 " " "     159      ##STR62##      H " " "     160 " CH.sub.3 " " "     161      ##STR63##      H " " "     162 " CH.sub.3 " " "     163      ##STR64##      H " " " [115-117]     164 " CH.sub.3 " " " n.sub.D      .sup.23 1.5717                                 165      ##STR65##      H " " " [104-106]     166 " CH.sub.3 " " "     167      ##STR66##      H CH.sub.3 N CN     168 " CH.sub.3 " " "     169      ##STR67##      H " " " [112-114]     170 " CH.sub.3 " " " n.sub.D      .sup.25 1.5413                                 171      ##STR68##      H " " " [122-124]     172 " CH.sub.3 " " " [143-144]      173 " " C.sub.2 H.sub.5 " " n.sub.D      .sup.25 1.5575                       174 " C.sub.2 H.sub.5 CH.sub.3 " "     [63-70]     175      ##STR69##      H " " " [149-151]     176 " CH.sub.3 " " "     177      ##STR70##      H H " " [179-183]     178 " CH.sub.3 " " " n.sub.D      .sup.25 1.5952                                 179      ##STR71##      H CH.sub.3 N CN     180 " CH.sub.3 " " "     181      ##STR72##      H " " "     182 " CH.sub.3 " " "     183      ##STR73##      H " " "     184 " CH.sub.3 " " "     185      ##STR74##      H " " "     186 " CH.sub.3 " " "     187      ##STR75##      H " " "     188 " CH.sub.3 " " " [106-109]     189      ##STR76##      H CH.sub.3 " " [90-92]     190      ##STR77##      CH.sub.3 CH.sub.3 N CN [102-103]     191      ##STR78##      H " " "     192 " CH.sub.3 " " "     193      ##STR79##      H H " "     194 " " CH.sub.3 " " [127-129]      195 " " CH.sub.2      Cl " "                                                  196 " "     CH.sub.2      F " "                                                            197 "     " C.sub.2      H.sub.5 " "             198 " "      ##STR80##      " "     199 " " CH.sub.2      SCH.sub.3 " "                                            200 " "     CH.sub.2      OCH.sub.3 " "            201      ##STR81##      H C.sub.3 H.sub.7 (n) N CN n.sub.D      .sup.25.5 1.5528                                        202 " CH.sub.3 H " "      203 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5798                            204 " " CH.sub.2 Cl " "          205 " " CH.sub.2      F " "                                               206 " H C.sub.2     H.sub.5 " " n.sub.D      .sup.25.5 1.5657                        207 " "      ##STR82##      " "     208 " " CH.sub.2      SCH.sub.3 " "                                            209 " "     CH.sub.2      OCH.sub.3 " "                                                    210 "     " C.sub.3 H.sub.7      (i) " "                                                 211 " " C.sub.4     H.sub.9      (t) " "           212      ##STR83##      C.sub.2      H.sub.5 H N CN            213 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.5665                      214 " " CH.sub.2      Cl " "            215 " " C.sub.2      H.sub.5 " "                            216 " C.sub.3 H.sub.7 (i) H " "       217 " " CH.sub.3 " "      218 " " C.sub.2      H.sub.5 " "                                              219 " COCH.sub.     3 H " "      220 " " CH.sub.3 " "      221 " SO.sub.2      CH.sub.3 H " "                                            222 " "     CH.sub.3 " "     223      ##STR84##      H H N NO.sub.2     224 " " CH.sub.3 " "      225 " " CH.sub.2      Cl " "                                                  226 " "     CH.sub.2      F " "                                                            227 "     " C.sub.2      H.sub.5 " "             228 " "      ##STR85##      " "     229 " " CH.sub.2      SCH.sub.3 " "                                            230 " "     CH.sub.2      OCH.sub.3 " "                                                    231 "     " C.sub.3 H.sub.7      (i) " "                                                 232 " " C.sub.4     H.sub.9      (t) " "                                                           233 "     " CHCH.sub.2       " "                 234 " "      ##STR86##      " "     235      ##STR87##      CH.sub.3 H N NO.sub.2     236 " " CH.sub.3 " " n.sub.D      .sup.25 1.5808                               237 " " CH.sub.2 Cl " "         238 " " CH.sub.2      F " "                                                239 " " C.sub.2     H.sub.5 " "     240 " "      ##STR88##      " "     241 " " CH.sub.2      SCH.sub.3 " "                                            242 " "     CH.sub.2      OCH.sub.3 " "                                                    243 "     " C.sub.3 H.sub.7      (n) " "                                                 244 " " C.sub.4     H.sub.9      (t) " "                                                           245 "     " CHCH.sub.2       " "                 246 " "      ##STR89##      " "     247      ##STR90##      C.sub.2      H.sub.5 H N NO.sub.2            248 " " CH.sub.3 " "      249 " " C.sub.2      H.sub.5 " "                                              250 " C.sub.3     H.sub.7      (i) H " "                                                         251 "     " CH.sub.3 " "      252 " " C.sub.2      H.sub.5 " "                     253 "      ##STR91##      H " "     254 " " CH.sub.3 " "      255 " " C.sub.2      H.sub.5 " "                                              256 " COCH.sub.     3 H " "      257 " " CH.sub.3 " "      258 " SO.sub.2      CH.sub.3 H " "                                            259 " "     CH.sub.3 " "     260      ##STR92##      H CH.sub.3 N NO.sub.2     261 " CH.sub.3 " " "     262      ##STR93##      H " " "     263 " CH.sub.3 " " "     264      ##STR94##      H " " "     265 " CH.sub.3 " " "     266      ##STR95##      H " " "     267 " CH.sub.3 " " "     268      ##STR96##      H " " "     269 " CH.sub.3 " " "     270      ##STR97##      H " " "     271 " CH.sub.3 " " "     272      ##STR98##      H CH.sub.3 N NO.sub.2     273 " CH.sub.3 " " "     274      ##STR99##      H " " "     275 " CH.sub.3 " " "     276      ##STR100##      H " " "     277 " CH.sub.3 " " "     278      ##STR101##      H " " "     279 " CH.sub.3 " " "     280      ##STR102##      H " " "     281 " CH.sub.3 " " "     282      ##STR103##      H " " "     283 " CH.sub.3 " " "     284      ##STR104##      H CH.sub.3 N NO.sub.2     285 " CH.sub.3 " " "     286      ##STR105##      H " " "     287 " CH.sub.3 " " "     288      ##STR106##      H " " "     289 " CH.sub.3 " " "     290      ##STR107##      H " " "     291 " CH.sub.3 " " "     292      ##STR108##      H " " "     293 " CH.sub.3 " " "     294      ##STR109##      H CH.sub.3 N NO.sub.2     295 " CH.sub.3 " " "     296      ##STR110##      H " " "     297 " CH.sub.3 " " "     298      ##STR111##      H " " "     299 " CH.sub.3 " " "     300      ##STR112##      H " " "     301 " CH.sub.3 " " "     302      ##STR113##      H " " "     303 " CH.sub.3 " " "     304      ##STR114##      H " " "     305      ##STR115##      CH.sub.3 CH.sub.3 N NO.sub.2     306      ##STR116##      H " " "     307 " CH.sub.3 " " "     308      ##STR117##      H " " "     309 " CH.sub.3 " " "     310      ##STR118##      H " " "     311 " CH.sub.3 " " "     312      ##STR119##      H " " "     313 " CH.sub.3 " " "     314      ##STR120##      H CH.sub.3 N NO.sub.2     315 " CH.sub.3 " " "     316      ##STR121##      H " " "     317 " CH.sub.3 " " "     318      ##STR122##      H " " "     319 " CH.sub.3 " " "      320 " " C.sub.2      H.sub.5 " "                                              321 " C.sub.2     H.sub.5 CH.sub.3 " "     322      ##STR123##      H " " "     323 " CH.sub.3 " " "     324      ##STR124##      H CH.sub.3 N NO.sub.2     325 " CH.sub.3 " " "     326      ##STR125##      H " " "     327 " CH.sub.3 " " "     328      ##STR126##      H " " "     329 " CH.sub.3 " " "     330      ##STR127##      H " " "     331 " CH.sub.3 " " "     332      ##STR128##      H " " "     333 " CH.sub.3 " " "     334      ##STR129##      H " " "     335 " CH.sub.3 " " "     336      ##STR130##      H H N NO.sub.2     337 " " CH.sub.3 " "      338 " " C.sub.2      H.sub.5 " "                                              339 " "     CH.sub.2      Cl " "                                                           340 "     " CH.sub.2      F " "              341 " "      ##STR131##      " "     342 " " CH.sub.2      SCH.sub.3 " "                                            343 " "     CH.sub.2      OCH.sub.3 " "            344      ##STR132##      CH.sub.3 H N NO.sub.2     345 " " CH.sub.3 " "      346 " " CH.sub.2      Cl " "                                                  347 " "     CH.sub.2      F " "                                                            348 "     " C.sub.2      H.sub.5 " "             349 " "      ##STR133##      " "     350 " " CH.sub.2      SCH.sub.3 " "                                            351 " "     CH.sub.2      OCH.sub.3 " "                                                    352 "     " C.sub.3 H.sub.7      (i) " "                                                 353 " " C.sub.4     H.sub.9      (t) " "           354      ##STR134##      C.sub.2      H.sub.5 H N NO.sub.2            355 " " CH.sub.3 " "      356 " " CH.sub.2      Cl " "                                                  357 " " C.sub.2     H.sub.5 " "      358 " C.sub.3 H.sub.7      (i) H " "                                          359 " " CH.sub.3 " "      360 " " C.sub.2      H.sub.5 " "                                              361 " COCH.sub.     3 H " "      362 " " CH.sub.3 " "      363 " SO.sub.2      CH.sub.3 H " "                                            364 " "     CH.sub.3 " "     365      ##STR135##      H H CH NO.sub.2 [116-118]     366 " " CH.sub.3 " " [133-135]      367 " " CH.sub.2      Cl " "                                                  368 " " C.sub.2     H.sub.5 " " [95-98]      369 " " C.sub.3 H.sub.7      (i) " " [150-152]                                370 " " C.sub.4     H.sub.7      (t) " "                                                           371 "     " CHCH.sub.2       " "                                                         372 " "     CHCHCH.sub.3 " "      373 " " CH.sub.2      CN " "                                                  374 " "     CH.sub.2      NO.sub.2 " "                                                     375 "     " CH.sub.2 COOC.sub.2      H.sub.5 " "                          376      ##STR136##      H      ##STR137##      CH NO.sub.2     377 " "      ##STR138##      " "     378 " "      ##STR139##      " "     379 " "      ##STR140##      " "     380 " CH.sub.3 H " "      381 " " CH.sub.3 " " [79-82]      382 " " CH.sub.2      Cl " "                                                  383 " " C.sub.2     H.sub.5 " " [101-104]      384 " " C.sub.3 H.sub.7      (i) " "                                          385 " " C.sub.4     H.sub.7      (t) " "                                                           386 "     " CHCH.sub.2       " "                                                         387 " "     CHCHCH.sub.3 " "     388      ##STR141##      CH.sub.3 CH.sub.2      CN CH NO.sub.2                       389 " " CH.sub.2      NO.sub.2 " "                           390 " " CH.sub.2 COOC.sub.2     H.sub.5 " "     391 " "      ##STR142##      " "     392 " "      ##STR143##      " "     393 " "      ##STR144##      " "     394 " "      ##STR145##      " "     395 " C.sub.2      H.sub.5 H " "                                               396 " "     CH.sub.3 " "      397 " " C.sub.2      H.sub.5 " "                                              398 " C.sub.3     H.sub.7      (i) H " "                                                         399 "     " CH.sub.3 " "     400      ##STR146##      C.sub.3 H.sub.7 (i) C.sub.2      H.sub.5 CH NO.sub.2                                 401 "      ##STR147##      H " "     402 " " CH.sub.3 " "      403 " " C.sub.2      H.sub.5 " "                                              404 " CH.sub.2     CHCH.sub.2       H " "                                                         405 " "     CH.sub.3 " "      406 " " C.sub.2      H.sub.5 " "                     407 "      ##STR148##      H " "     408 " " CH.sub.3 " "      409 " " C.sub.2      H.sub.5 " "                                              410 " CHO H "     "      411 " " CH.sub.3 " "     412      ##STR149##      CHO C.sub.2      H.sub.5 CH NO.sub.2                 413 " COCH.sub.3 H " "      414 " " CH.sub.3 " "      415 " " C.sub.2      H.sub.5 " "                                              416 " SO.sub.2     CH.sub.3 H " "      417 " " CH.sub.3 " "      418 " " C.sub.2      H.sub.5 " "                                              419 " COOC.sub.     2      H.sub.5 H " "     420 " " CH.sub.3 " "      421 " " C.sub.2      H.sub.5 " "                                              422 " OC.sub.2     H.sub.5 H " "      423 " " CH.sub.3 " "      424 " " C.sub.2      H.sub.5 " "                                              425 " CH.sub.2     CCH H " "      426 " " CH.sub.3 " "      427 " " C.sub.2      H.sub.5 " "                     428      ##STR150##      H CH.sub.3 CH NO.sub.2     429 " CH.sub.3 " " "     430      ##STR151##      H " " "     431 " CH.sub.3 " " "     432      ##STR152##      H " " "     433 " CH.sub.3 " " "     434      ##STR153##      H " " "     435 " CH.sub.3 " " "     436      ##STR154##      H " " "     437 " CH.sub.3 " " "     438      ##STR155##      H " " "     439 " CH.sub.3 " " "     440      ##STR156##      H CH.sub.3 CH NO.sub.2     441 " CH.sub.3 " " "     442      ##STR157##      H " " "     443 " CH.sub.3 " " "     444      ##STR158##      H " " "     445 " CH.sub.3 " " "     446      ##STR159##      H " " "     447 " CH.sub.3 " " "     448      ##STR160##      H " " "     449 " CH.sub.3 " " "     450      ##STR161##      H " " "     451 " CH.sub.3 " " "     452      ##STR162##      H CH.sub.3 CH NO.sub.2     453 " CH.sub.3 " " "     454      ##STR163##      H " " "     455 " CH.sub.3 " " "     456      ##STR164##      H " " "     457 " CH.sub.3 " " "     458      ##STR165##      H " " "     459 " CH.sub.3 " " "     460      ##STR166##      H " " "     461 " CH.sub.3 " " "     462      ##STR167##      H CH.sub.3 CH NO.sub.2     463 " CH.sub.3 " " "     464      ##STR168##      H " " "     465 " CH.sub.3 " " "     466      ##STR169##      H " " "     467 " CH.sub.3 " " "     468      ##STR170##      H " " "     469 " CH.sub.3 " " "     470      ##STR171##      H " " "     471 " CH.sub.3 " " "     472      ##STR172##      H " " "     473      ##STR173##      CH.sub.3 CH.sub.3 CH NO.sub.2     474      ##STR174##      H " " "     475 " CH.sub.3 " " "     476      ##STR175##      H " " "     477 " CH.sub.3 " " "     478      ##STR176##      H " " "     479 " CH.sub.3 " " "     480      ##STR177##      H " " "     481 " CH.sub.3 " " "     482      ##STR178##      H " " "     483 " CH.sub.3 " " "     484      ##STR179##      H CH.sub.3 CH NO.sub.2     485 " CH.sub.3 " " "     486      ##STR180##      H " " "     487 " CH.sub.3 " " "      488 " " C.sub.2      H.sub.5 " "                                              489 " C.sub.2     H.sub.5 CH.sub.3 " "     490      ##STR181##      H " " "     491 " CH.sub.3 " " "     492      ##STR182##      H " " "     493 " CH.sub.3 " " "     494      ##STR183##      H " " "     495 " CH.sub.3 " " "     496      ##STR184##      H CH.sub.3 CH NO.sub.2     497 " CH.sub.3 " " "     498      ##STR185##      H " " "     499 " CH.sub.3 " " "     500      ##STR186##      H " " "     501 " CH.sub.3 " " "     502      ##STR187##      H H CH NO.sub.2     503 " " CH.sub.3 " "      504 " " CH.sub.2      Cl " "                                                  505 " " C.sub.2     H.sub.5 " "      506 " " C.sub.3 H.sub.7      (i) " "                                          507 " " C.sub.4     H.sub.9      (t) " "                                                           508 "     CH.sub.3 H " "      509 " " CH.sub.3 " "      510 " " CH.sub.2      Cl " "                                                  511 " " C.sub.2     H.sub.5 " "     512 " "      ##STR188##      " "     513      ##STR189##      CH.sub.3 C.sub.3 H.sub.7      (i) CH NO.sub.2                              514 " " C.sub.4 H.sub.9      (t) " "                  515 " C.sub.2      H.sub.5 H " "                     516 " " CH.sub.3 " "      517 " " C.sub.2      H.sub.5 " "                     518 "      ##STR190##      H " "     519 " " CH.sub.3 " "      520 " " C.sub.2      H.sub.5 " "                                              521 " COCH.sub.     3 H " "      522 " " CH.sub.3 " "      523 " " C.sub.2      H.sub.5 " "                                              524 " SO.sub.2     CH.sub.3 H " "      525 " " CH.sub.3 " "      526 " " C.sub.2      H.sub.5 " "                     527      ##STR191##      H H CH CN     528 " " CH.sub.3 " " [95-98]      529 " " CH.sub.2      Cl " "                                                  530 " " C.sub.2     H.sub.5 " "      531 " " C.sub.3 H.sub.7      (i) " "                                          532 " " C.sub.4     H.sub.9      (t) " "                                                           533 "     " CHCH.sub.2       " "                                                         534 " "     CHCHCH.sub.3 " "      535 " " CH.sub.2      CN " "                                                  536 " "     CH.sub.2      NO.sub.2 " "                                                     537 "     " CH.sub.2 COOC.sub.2      H.sub.5 " "                          538      ##STR192##      H      ##STR193##      CH CN     539 " "      ##STR194##      " "     540 " "      ##STR195##      " "     541 " "      ##STR196##      " "     542 " CH.sub.3 H " "      543 " " CH.sub.3 " " n.sub.D      .sup.29 1.5941                              544 " " CH.sub.2 Cl " "          545 " " C.sub.2      H.sub.5 " "                                          546 " " C.sub.3     H.sub.7      (i) " "                                                           547 "     " C.sub.4 H.sub.9      (t) " "                                                 548 " "     CHCH.sub.2       " "                                                           549 " "     CHCHCH.sub.3 " "     550      ##STR197##      CH.sub.3 CH.sub.2      CN CH CN                       551 " " CH.sub.2      NO.sub.2 " "                           552 " " CH.sub.2 COOC.sub.2     H.sub.5 " "     553 " "      ##STR198##      " "     554 " "      ##STR199##      " "     555 " "      ##STR200##      " "     556 " "      ##STR201##      " "     557 " C.sub.2      H.sub.5 H " "                                               558 " "     CH.sub.3 " "      559 " " C.sub.2      H.sub.5 " "                                              560 " C.sub.3     H.sub.7      (i) H " "                                                         561 "     " CH.sub.3 " "     562      ##STR202##      C.sub.3 H.sub.7 (i) C.sub.2      H.sub.5 CH CN                                 563 "      ##STR203##      H " "     564 " " CH.sub.3 " "      565 " " C.sub.2      H.sub.5 " "                                              566 " CH.sub.2     CHCH.sub.2       H " "                                                         567 " "     CH.sub.3 " "      568 " " C.sub.2      H.sub.5 " "                     569 "      ##STR204##      H " "     570 " " CH.sub.3 " "      571 " " C.sub.2      H.sub.5 " "                                              572 " CHO H "     "      573 " " CH.sub.3 " "     574      ##STR205##      CHO C.sub.2      H.sub.5 CH CN                 575 " COCH.sub.3 H " "      576 " " CH.sub.3 " "      577 " " C.sub.2      H.sub.5 " "                                              578 " SO.sub.2     CH.sub.3 H " "      579 " " CH.sub.3 " "      580 " " C.sub.2      H.sub.5 " "                                              581 " COOC.sub.     2      H.sub.5 H " "     582 " " CH.sub.3 " "      583 " " C.sub.2      H.sub.5 " "                                              584 " OC.sub.2     H.sub.5 H " "      585 " " CH.sub.3 " "      586 " " C.sub.2      H.sub.5 " "                                              587 " CH.sub.2     CCH H " "      588 " " CH.sub.3 " "      589 " " C.sub.2      H.sub.5 " "                     590      ##STR206##      H CH.sub.3 CH CN     591 " CH.sub.3 " " "     592      ##STR207##      H " " "     593 " CH.sub.3 " " "     594      ##STR208##      H " " "     595 " CH.sub.3 " " "     596      ##STR209##      H " " "     597 " CH.sub.3 " " "     598      ##STR210##      H " " "     599 " CH.sub.3 " " "     600      ##STR211##      H " " "     601 " CH.sub.3 " " "     602      ##STR212##      H CH.sub.3 CH CN     603 " CH.sub.3 " " "     604      ##STR213##      H " " "     605 " CH.sub.3 " " "     606      ##STR214##      H " " "     607 " CH.sub.3 " " "     608      ##STR215##      H " " "     609 " CH.sub.3 " " "     610      ##STR216##      H " " "     611 " CH.sub.3 " " "     612      ##STR217##      H " " "     613 " CH.sub.3 " " "     614      ##STR218##      H CH.sub.3 CH CN     615 " CH.sub.3 " " "     616      ##STR219##      H " " "     617 " CH.sub.3 " " "     618      ##STR220##      H " " "     619 " CH.sub.3 " " "     620      ##STR221##      H " " "     621 " CH.sub.3 " " "     622      ##STR222##      H " " "     623 " CH.sub.3 " " "     624      ##STR223##      H CH.sub.3 CH CN     625 " CH.sub.3 " " "     626      ##STR224##      H " " "     627 " CH.sub.3 " " "     628      ##STR225##      H " " "     629 " CH.sub.3 " " "     630      ##STR226##      H " " "     631 " CH.sub.3 " " "     632      ##STR227##      H " " "     633 " CH.sub.3 " " "     634      ##STR228##      H " " "     635      ##STR229##      CH.sub.3 CH.sub.3 CH CN     636      ##STR230##      H " " "     637 " CH.sub.3 " " "     638      ##STR231##      H " " "     639 " CH.sub.3 " " "     640      ##STR232##      H " " "     641 " CH.sub.3 " " "     642      ##STR233##      H " " "     643 " CH.sub.3 " " "     644      ##STR234##      H CH.sub.3 CH CN     645 " CH.sub.3 " " "     646      ##STR235##      H " " "     647 " CH.sub.3 " " "     648      ##STR236##      H " " "     649 " CH.sub.3 " " "      650 " " C.sub.2      H.sub.5 " "                                              651 " C.sub.2     H.sub.5 CH.sub.3 " "     652      ##STR237##      H CH.sub.3 CH CN     653 " CH.sub.3 " " "     654      ##STR238##      H " " "     655 " CH.sub.3 " " "     656      ##STR239##      H " " "     657 " CH.sub.3 " " "     658      ##STR240##      H " " "     659 " CH.sub.3 " " "     660      ##STR241##      H " " "     661 " CH.sub.3 " " "     662      ##STR242##      H " " "     663 " CH.sub.3 " " "     664      ##STR243##      H H CH CN     665 " " CH.sub.3 " "      666 " " CH.sub.2      Cl " "                                                  667 " " C.sub.2     H.sub.5 " "      668 " " C.sub.3 H.sub.7      (i) " "                                          669 " " C.sub.4     H.sub.9      (t) " "                                                           670 "     CH.sub.3 H " "      671 " " CH.sub.3 " "      672 " " CH.sub.2      Cl " "                                                  673 " " C.sub.2     H.sub.5 " "     674 " "      ##STR244##      " "     675      ##STR245##      CH.sub.3 C.sub.3 H.sub.7      (i) CH CN                              676 " " C.sub.4 H.sub.9      (t) " "                  677 " C.sub.2      H.sub.5 H " "                     678 " " CH.sub.3 " "      679 " " C.sub.2      H.sub.5 " "                     680 "      ##STR246##      H " "     681 " " CH.sub.3 " "      682 " " C.sub.2      H.sub.5 " "                                              683 " COCH.sub.     3 H " "      684 " " CH.sub.3 " "      685 " " C.sub.2      H.sub.5 " "                                              686 " SO.sub.2     CH.sub.3 H " "     687      ##STR247##      SO.sub.2      CH.sub.3 CH.sub.3 CH CN             688 " " C.sub.2      H.sub.5 " "     *1 .sup.1 HNMR(CDCl.sub.3) δ; ppm 3.32 (s, 3H), 4.63 (s, 2H), 7.37     (d, 1H), 7.62 (dd, 1H), 8.37 (d, 1H)

Further, the following compound is described in U.S. Pat. No. 4,918,088,which has insecticidal activities. ##STR248## The compound however showsno insecticidal activity against lepidopterous insects and green riceleafhopper which are more serious pests on crops, though it shows someactivity against cotton aphid.

The purpose of this invention is to provide agricultural chemicals whichcan be advantageously synthesized industrially, have certain effects andmay be applied safely.

The compound of this invention has high insecticidal activity againstboth lepidopterous and hemipterous insects.

SUMMARY OF THE INVENTION

The present invention relates to a compound having the formula##STR249## wherein R₁ represents an optionally substituted 5-6 memberedaromatic hetero ring containing nitrogen atom, except a non-substituted2-pyridyl;

X represents an optionally substituted C₁₋₃ alkylene or alkylidene;

R₂ represents a hydrogen, a carbamoyl, a mono or di C₁₋₅ alkylcarbamoyl, a thiocarbamoyl, a mono or di C₁ alkylthiocarbamoyl, asulfamoyl, a mono or di C₁ alkylsulfamoyl, an optionally substitutedC₁₋₅ alkyl, an optionally substituted C₂₋₅ alkenyl, an optionallysubstituted C₂₋₅ alkynyl, an optionally substituted C₃₋₈ cycloalkyl, anoptionally substituted C₃₋₈ cycloalkenyl, an optionally substituted arylor --Y--R₅ ;

Y represents O, S(O)_(n), CO, CS or CO₂ ;

n represents 0,1 or 2;

R₅ represents a hydrogen, an optionally substituted C₁₋₅ alkyl, anoptionally substituted C₂₋₅ alkenyl, an optionally substituted C₂₋₅alkynyl, an optionally substituted C₃₋₈ cycloalkyl, an optionallysubstituted C₃₋₈ cycloalkenyl or an optionally substituted aryl;

R₃ represents a hydrogen, an optionally substituted C₁₋₅ alkyl, anoptionally substituted C₂₋₅ alkenyl, an optionally substituted C₂₋₅alkynyl, an optionally substituted C₃₋₈ cycloalkyl or an optionallysubstituted C₃₋₈ cycloalkenyl;

R₄ represents a cyano or a nitro; and Z represents CH or N; or its salt.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of this invention can be prepared in accordance with thefollowing reaction schemes:

(1) Preparation Method 1: ##STR250## where r¹ and r² represent a C₁₋₅alkyl; and R₁, R₂, R₃, R₄ and X are as defined above.

The reaction is carried out in an inactive organic solvent, preferablyin an aromatic hydrocarbon solvent such as xylene, toluene or benzene,in the presence of acidic catalyst such as p-toluenesulfonic acid, ifnecessary, under reflux.

(2) Preparation method 2: ##STR251## where r³ represents a C₁₋₅ alkyl:and R₁, R₂, R₃ and X are as defined above. This reaction is carried outin an inactive organic solvent, preferably in an alcohol such asmethanol, ethanol, between room temperature and the boiling point of theused solvent.

(3) Preparation Method 3: ##STR252## where Hal represents a halogen; andR₁, R₂, R₃ and X are as defined above.

This reaction is carried out in an inactive organic solvent, preferablyDMF, THF, benzene acetonitrile, acetone, methylethylketone, in thepresence of acid accepter such as potassium carbonate, NaH,triethylamine, between room temparature and the boiling point of theused solvent.

(4) Preparation Method 4: ##STR253## where R₁, R₂, R₃, X and Hal are asdefined above. This reaction is carried out in the same manner as thatof Preparation Method 3.

(5) Preparation Method 5: ##STR254## where R₁, R₂, R₃ and X are asdefined above. This reaction is carried out in an inactive organicsolvent, preferably acetonitrile, carbon tetrachloride, dichloroethane,in the presence of nitration reagent such as nitroniumtetrafluoroborate, between -20° C. and the boiling point of the usedsolvent.

After the reaction is completed, an usual after-treatment gives theintended compound. The structure of the compounds of this invention wasdetermined by such means as IR, NMR, MASS, etc. When R₂ is hydrogen in acompound of this invention, tautomers represented by ##STR255## canexist.

The syn--aniti isomers, when Z represents N, and the cis-trans isomers,when Z represents CH, as represented by, ##STR256## can also exist.

The ratio varies depending on e.g. conditions of instrumental analysis.

EXAMPLES

The following examples illustrate the present invention.

Example 1 2-(2-chloro-5-pyridylmethylamino)-1-nitro-1-butene: ##STR257##In 50 ml of toluene, 4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of1-nitro-2-butanone and 0.1 g of p-toluene sulfonic acid were mixed andthe mixture was refluxed for 2 hours. The solvent was then distilled offand the residue was purified by column chromatography on silica gel toafford 4.1 g of compound No. 368. m.p. 95°-98° C. Example 22-(2-chloro-5-pyridylmethylamino)-1-cyano-1-propene: ##STR258## 1.4 g of2-chloro-5-pyridylmethylamine and 0.8 g of 1-cyano-2-propanone weremixed and the mixture was stirred at room temperature over night. Thesolvent was then distilled off and the residue was purified by columnchromatography on silica gel to afford 1.7 g of compound No. 528. m.p.95°-98° C. EXAMPLE 3N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine: ##STR259##In 20 ml of ethanol, 1.6 g of N-methyl-2-cloro-5-pyridylmethylamine and1.2 g of ethyl-N-cyanoacetamidine were mixed and the mixture was stirredat room temperature over night. The solvent was then distilled off andthe residue was purified by column chromatography on silica gel toafford 1.8 g of compound No. 22. m.p. 101°-103° C. EXAMPLE 4N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine: ##STR260##0.7 g of sodium hydride (purity 60%) was added to the solution of 3.0 gof N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine in 20 ml ofN.N-dimthylformamide at ice bath temperature. After stirring it at thesame temperature for 1 hour, 2.7 g of ethyl iodide was added to themixture, followed by stirring for 5 hours at room temperature. Thereaction mixture was then poured into ice-water, extracted with ethylacetate, dried over anhydrous magnesium sulfate and concentrated underreduced pressre. The residue obtained was purified by columnchromatography on silica gel to afford 1.6 g of compound No. 51. m.p.100°-101° C. EXAMPLE 5N-cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine: ##STR261##0.6 g of sodium hydride (purity 60%) was added to the solution of 1.3 gof N-cyano-N'-methylacetamidine in 20 ml of N,N-dimethylformamide at icebath temperature. After stirring it at the same temperature for 1 hour,2.2 g of 2-chloro-5-pyridylmethylchlride was added to the mixture,followed by stirring for 5 hours at room temperature. The reactionmixture was then poured into ice-water, extrated with ethyl acetate,dried over anhydrous magnesium sulfate and concentrated under reducedpressre. The residue obtained was purified by column chromatography onsilica gel to afford 1.5 g of compound No. 22 m.p. 101-°103° C.Reference Example N-(2-chloro-5-pyridylmethyl)-N-methylacetamidinehydrochloride: ##STR262## To 40 ml of ethanol was added 5.1 g ofN-(2-chloro-5-pyridylmethyl)-N-Methylamine and then 4 g of ethylacetimidate hydrochloride at 0° C. After stirring for an hour, thereaction mixture was allowed to warm to room temperature and stirredover night. The solvent was then distilled off. The obtained whiteresidue was washed with diethyl ether to afford 7.3 g of the titlecompound m.p. 192-°197° C. Example 6N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine: ##STR263## Toa suspension of 1 g of N-(2-chloro-5-pyridylmethyl)-N-methylamidinehydrochloride in 10 ml of dry acetonitrile was added dropwise 0.7 g ofDBU under nitrogen at room temperature. After stirring for 30 minutes,the solution was added dropwise to a suspension of 0.6 g of nitroniumtetrafluoroborate in 5 ml of dry acetonitrile under nitrogen on coolingwith ice-water and let stir for 4 hours. After which time, the mixturewas poured into ice-water, then extracted several time with chloroform.The combined chloroform layer was dried over magnesium sulfate, filteredand distilled off. The crude oil was purified by column chromatgraphy onsilica gel to afford 0,3 g of compound No. 236.

    N.sub.D.sup.25 1.5808

Typical examples of this invention including those described above arelisted in Table 1.

    TABLE 1      - Structure Formula      ##STR264##                                                                              C     ompound No. R.sub.1 X R.sub.2 R.sub.3 Z R.sub.4 Physical Properties [ ]     m.p. °C.      1     ##STR265##      H H N CN [123-126]      2 " " CH.sub.3 " " [141-143]       3 " " CH.sub.2      Cl " " [124-126]                                          4 " "     CH.sub.2      F " " [151-152]                                                   5 " "     CF.sub.3 " " [112-114]       6 " " C.sub.2      H.sub.5 " " [120-122]                                      7 " "     C.sub.3 H.sub.7      (n) " " [100-101]      8 " "     ##STR266##      " " [193.5-195]                       9 " " C.sub.4 H.sub.9      (t) " "                            10 " " CH.sub.2 OCH.sub.3 " "     [128-128.5]       11 " " CH.sub.2      SCH.sub.3 " " [116-118]      12     ##STR267##      " CH.sub.2 COOC.sub.2 H.sub.5 N CN n.sub.D      .sup.25.5 1.5608                                                 13 " " CH.sub.2 CH.sub.2     COOC.sub.2      H.sub.5 " "                                                     14 " "     CH.sub.2      NHCH.sub.3 " "                                                    15 "     " CH.sub.2      N(CH.sub.3).sub.2 " "                                           16 " "     CH.sub.2 CH.sub.2 CH.sub.2      Cl " " [114-115]      17 " "     ##STR268##      " " [190-191]      18 " " CH.sub.2      CN " " [106-108]                                          19 " "     CH.sub.2 CH.sub.2      CN " "      20 " "     ##STR269##      " " [187-189]      21 " CH.sub.3 H " " n.sub.D      .sup.25 1.5918                                22 " " CH.sub.3 " "     [101-103]      23 " " " " " [161-162]           HCl salt       24 " " CH.sub.2 Cl " " n.sub.D      .sup.26.5 1.5921                          25 " " CH.sub.2 F " " [79-80]      26 " " CF.sub.3 " " *1      27     ##STR270##      CH.sub.3 C.sub.2 H.sub.5 N CN n.sub.D      .sup.27 1.5742                                            28 " " C.sub.3 H.sub.7 (n) " "     [97-100]      29 " "     ##STR271##      " " n.sub.D      .sup.24.5 1.5829                  30 " " C.sub.4 H.sub.9      (t) " "                                31 " " CH.sub.2 OCH.sub.3 " "     n.sub.D      .sup.24 1.5803                                                     32 "     " CH.sub.2 SCH.sub.3 " " n.sub.D      .sup.24.5 1.6070                          33 " " CH.sub.2 COOC.sub.2     H.sub.5 " " n.sub.D      .sup.25.5 1.5604                                       34 " " CH.sub.2     CH.sub.2 COOC.sub.2 H.sub.5 " " n.sub.D      .sup.24.5 1.5605                   35 " " CH.sub.2 NHCH.sub.3 " "     n.sub.D      .sup.25 1.5861                                                     36 "     " CH.sub.2 N(CH.sub.3).sub.2 " " n.sub.D      .sup.25 1.5577                    37 " " CH.sub.2 CH.sub.2 Cl " "             38 " " CH.sub.2 CH.sub.2 CH.sub.2 Cl " " n.sub.D .sup.25.5     1.5830      39 " "     ##STR272##      " "      40 " "     ##STR273##      " "      41 " "     ##STR274##      " " n.sub.D      .sup.25.5 1.6040      42     ##STR275##      CH.sub.3 CHCH.sub.2       N CN                          43 " " CH.sub.2 CN " " n.sub.D .sup.25 1.5913             44 " " CH.sub.2 CH.sub.2      CN " " [112-114]      45 " "     ##STR276##      " "      46 " "     ##STR277##      " " [224-226]      47 " CHF.sub.2 H " "       48 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.5423                             49 " " C.sub.2 H.sub.5 " "       50 " C.sub.2      H.sub.5 H " " [101-103]                                     51 " "     CH.sub.3 " " [100-101]       52 " " C.sub.2      H.sub.5 " "                                               53 " C.sub.3     H.sub.7      (i) H " " [205-207]                                                54 "     " CH.sub.3 " "       55 " " C.sub.2      H.sub.5 " "      56 "     ##STR278##      H " "      57     ##STR279##      ##STR280##      CH.sub.3 N CN n.sub.D      .sup.25 1.5825                            58 " " C.sub.2      H.sub.5 " "                          59 " CH.sub.2 OCH.sub.3 H " "            60 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5711                        61 " CH.sub.2 SCH.sub.3 H " "         62 " " CH.sub.3 " " n.sub.D      .sup.25 1.5828                             63 " CH.sub.2 COOC.sub.2     H.sub.5 H " "       64 " " CH.sub.3 " " n.sub.D      .sup.25 1.5475      65 "     ##STR281##      H " "      66 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5928      67 "     ##STR282##      H " "      68 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6155      69 "     ##STR283##      H " "      70 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.6093      71 "     ##STR284##      H " "      72     ##STR285##      ##STR286##      CH.sub.3 N CN [112-114]      73 " CH.sub.2 CHCH.sub.2  H " " n.sub.D      .sup.25 1.5841                    74 " " CH.sub.3 " " n.sub.D .sup.25     1.5809       75 " CH.sub.2      CCH H " "                                                  76 " "     CH.sub.3 " " n.sub.D      .sup.25.5 1.5730                                      77 " CH.sub.2 CN     H " "      78 " " CH.sub.3 " " [127-128]      79 "     ##STR287##      H " "      80 " " CH.sub.3 " " [124-127]      81 "     ##STR288##      H " "      82 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.6045      83 "     ##STR289##      H " "      84 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6092      85 "     ##STR290##      H " "      86     ##STR291##      ##STR292##      CH.sub.3 N CN n.sub.D      .sup.25.5 1.5910      87 "     ##STR293##      H " "      88 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.6162      89 "     ##STR294##      H " "      90 " " CH.sub.3 " " [115-117]      91 " OCH.sub.3 H " "      92 " " CH.sub.3 " " [110-112]      93 " CHO H " "      94 " " CH.sub.3 " "       95 " COCH.sub.3 H " " n.sub.D      .sup.25.5 1.5475                           96 " " CH.sub.3 " " [84-86]        97 " SO.sub.2      CH.sub.3 H " " [160-163]                                  98 " "     CH.sub.3 " "      99 "     ##STR295##      H " "     100 " " CH.sub.3 " " [112-114]     101      ##STR296##      COOC.sub.2      H.sub.5 H N CN                102 " " CH.sub.3 " " n.sub.D      .sup.25 1.5540                    103 " CONH.sub.2 H " "      104 " " CH.sub.3 " "     105 "      ##STR297##      H " "     106 " " CH.sub.3 " " [89-91]      107 " CONHCH.sub.3 H " "      108 " " CH.sub.3 " "      109 " CSNHCH.sub.3 H " "      110 " " CH.sub.3 " "     111      ##STR298##      H CH.sub.3 " "     112 " CH.sub.3 " " "     113      ##STR299##      H " " "     114 " CH.sub.3 " " "     115      ##STR300##      H " " " [83-85]     116      ##STR301##      CH.sub.3 CH.sub.3 N CN [76-78]     117      ##STR302##      H " " "     118 " CH.sub.3 " " " [145-147]     119      ##STR303##      H " " "     120 " CH.sub.3 " " " n.sub.D      .sup.25 1.5202                                 121      ##STR304##      H " " "     122 " CH.sub.3 " " "     123      ##STR305##      H " " "     124 " CH.sub.3 " " " n.sub.D      .sup.25.5 1.5580                                 125      ##STR306##      H " " "     126 " CH.sub.3 " " "     127      ##STR307##      H " " "     128 " CH.sub.3 " " "     129      ##STR308##      H " " " [162-163]     130 " CH.sub.3 " " " [105-107]     131      ##STR309##      H CH.sub.3 N CN     132 " CH.sub.3 " " " [138-139]     133      ##STR310##      H " " "     134 " CH.sub.3 " " " n.sub.D      .sup.25 1.5841                                 135      ##STR311##      H " " "     136 " CH.sub.3 " " " [107-109]     137      ##STR312##      H " " "     138 " CH.sub.3 " " "     139      ##STR313##      H " " "     140 " CH.sub.3 " " "     141      ##STR314##      H " " "     142 " CH.sub.3 " " "     143      ##STR315##      H " " " [122-124]     144 " CH.sub.3 " " " [110-113]     145      ##STR316##      H CH.sub.3 N CN [66-68]     146 " CH.sub.3 " " " n.sub.D      .sup.24.5 1.5790                                 147      ##STR317##      H " " "     148 " CH.sub.3 " " " [94-96]     149      ##STR318##      H " " " [130-132]     150 " CH.sub.3 " " " n.sub.D      .sup.25 1.5612                                 151      ##STR319##      H " " " [96-99]     152 " CH.sub.3 " " " n.sub.D      .sup.25.5 1.5800                                 153      ##STR320##      H " " "     154 " CH.sub.3 " " "     155      ##STR321##      H " " "     156      ##STR322##      CH.sub.3 CH.sub.3 N CN     157      ##STR323##      H " " "     158 " CH.sub.3 " " "     159      ##STR324##      H " " "     160 " CH.sub.3 " " "     161      ##STR325##      H " " "     162 " CH.sub.3 " " "     163      ##STR326##      H " " " [115-117]     164 " CH.sub.3 " " " n.sub.D      .sup.23 1.5717                                 165      ##STR327##      H " " " [104-106]     166 " CH.sub.3 " " "     167      ##STR328##      H CH.sub.3 N CN     168 " CH.sub.3 " " "     169      ##STR329##      H " " " [112-114]     170 " CH.sub.3 " " " n.sub.D      .sup.25 1.5413                                 171      ##STR330##      H " " " [122-124]     172 " CH.sub.3 " " " [143-144]      173 " " C.sub.2 H.sub.5 " " n.sub.D      .sup.25 1.5575                       174 " C.sub.2 H.sub.5 CH.sub.3 " "     [63-70]     175      ##STR331##      H " " " [149-151]     176 " CH.sub.3 " " "     177      ##STR332##      H H " " [179-183]     178 " CH.sub.3 " " " n.sub.D      .sup.25 1.5952                                 179      ##STR333##      H CH.sub.3 N CN     180 " CH.sub.3 " " "     181      ##STR334##      H " " "     182 " CH.sub.3 " " "     183      ##STR335##      H " " "     184 " CH.sub.3 " " "     185      ##STR336##      H " " "     186 " CH.sub.3 " " "     187      ##STR337##      H " " "     188 " CH.sub.3 " " " [106-109]     189      ##STR338##      H CH.sub.3 " " [90-92]     190      ##STR339##      CH.sub.3 CH.sub.3 N CN [102-103]     191      ##STR340##      H " " "     192 " CH.sub.3 " " "     193      ##STR341##      H H " "     194 " " CH.sub.3 " " [127-129]      195 " " CH.sub.2      Cl " "                                                  196 " "     CH.sub.2      F " "                                                            197 "     " C.sub.2      H.sub.5 " "             198 " "      ##STR342##      " "     199 " " CH.sub.2      SCH.sub.3 " "                                            200 " "     CH.sub.2      OCH.sub.3 " "            201      ##STR343##      H C.sub.3 H.sub.7 (n) N CN n.sub.D      .sup.25.5 1.5528                                        202 " CH.sub.3 H " "      203 " " CH.sub.3 " " n.sub.D      .sup.25.5 1.5798                            204 " " CH.sub.2 Cl " "          205 " " CH.sub.2      F " "                                               206 " H C.sub.2     H.sub.5 " " n.sub.D      .sup.25.5 1.5657                        207 " "      ##STR344##      " "     208 " " CH.sub.2      SCH.sub.3 " "                                            209 " "     CH.sub.2      OCH.sub.3 " "                                                    210 "     " C.sub.3 H.sub.7      (i) " "                                                 211 " " C.sub.4     H.sub.9      (t) " "           212      ##STR345##      C.sub.2      H.sub.5 H N CN            213 " " CH.sub.3 " " n.sub.D      .sup.24.5 1.5665                      214 " " CH.sub.2      Cl " "            215 " " C.sub.2      H.sub.5 " "                            216 " C.sub.3 H.sub.7 (i) H " "       217 " " CH.sub.3 " "      218 " " C.sub.2      H.sub.5 " "                                              219 " COCH.sub.     3 H " "      220 " " CH.sub.3 " "      221 " SO.sub.2      CH.sub.3 H " "                                            222 " "     CH.sub.3 " "     223      ##STR346##      H H N NO.sub.2     224 " " CH.sub.3 " "      225 " " CH.sub.2      Cl " "                                                  226 " "     CH.sub.2      F " "                                                            227 "     " C.sub.2      H.sub.5 " "             228 " "      ##STR347##      " "     229 " " CH.sub.2      SCH.sub.3 " "                                            230 " "     CH.sub.2      OCH.sub.3 " "                                                    231 "     " C.sub.3 H.sub.7      (i) " "                                                 232 " " C.sub.4     H.sub.9      (t) " "                                                           233 "     " CHCH.sub.2       " "                 234 " "      ##STR348##      " "     235      ##STR349##      CH.sub.3 H N NO.sub.2     236 " " CH.sub.3 " " n.sub.D      .sup.25 1.5808                               237 " " CH.sub.2 Cl " "         238 " " CH.sub.2      F " "                                                239 " " C.sub.2     H.sub.5 " "     240 " "      ##STR350##      " "     241 " " CH.sub.2      SCH.sub.3 " "                                            242 " "     CH.sub.2      OCH.sub.3 " "                                                    243 "     " C.sub.3 H.sub.7      (n) " "                                                 244 " " C.sub.4     H.sub.9      (t) " "                                                           245 "     " CHCH.sub.2       " "                 246 " "      ##STR351##      " "     247      ##STR352##      C.sub.2      H.sub.5 H N NO.sub.2            248 " " CH.sub.3 " "      249 " " C.sub.2      H.sub.5 " "                                              250 " C.sub.3     H.sub.7      (i) H " "                                                         251 "     " CH.sub.3 " "      252 " " C.sub.2      H.sub.5 " "                     253 "      ##STR353##      H " "     254 " " CH.sub.3 " "      255 " " C.sub.2      H.sub.5 " "                                              256 " COCH.sub.     3 H " "      257 " " CH.sub.3 " "      258 " SO.sub.2      CH.sub.3 H " "                                            259 " "     CH.sub.3 " "     260      ##STR354##      H CH.sub.3 N NO.sub.2     261 " CH.sub.3 " " "     262      ##STR355##      H " " "     263 " CH.sub.3 " " "     264      ##STR356##      H " " "     265 " CH.sub.3 " " "     266      ##STR357##      H " " "     267 " CH.sub.3 " " "     268      ##STR358##      H " " "     269 " CH.sub.3 " " "     270      ##STR359##      H " " "     271 " CH.sub.3 " " "     272      ##STR360##      H CH.sub.3 N NO.sub.2     273 " CH.sub.3 " " "     274      ##STR361##      H " " "     275 " CH.sub.3 " " "     276      ##STR362##      H " " "     277 " CH.sub.3 " " "     278      ##STR363##      H " " "     279 " CH.sub.3 " " "     280      ##STR364##      H " " "     281 " CH.sub.3 " " "     282      ##STR365##      H " " "     283 " CH.sub.3 " " "     284      ##STR366##      H CH.sub.3 N NO.sub.2     285 " CH.sub.3 " " "     286      ##STR367##      H " " "     287 " CH.sub.3 " " "     288      ##STR368##      H " " "     289 " CH.sub.3 " " "     290      ##STR369##      H " " "     291 " CH.sub.3 " " "     292      ##STR370##      H " " "     293 " CH.sub.3 " " "     294      ##STR371##      H CH.sub.3 N NO.sub.2     295 " CH.sub.3 " " "     296      ##STR372##      H " " "     297 " CH.sub.3 " " "     298      ##STR373##      H " " "     299 " CH.sub.3 " " "     300      ##STR374##      H " " "     301 " CH.sub.3 " " "     302      ##STR375##      H " " "     303 " CH.sub.3 " " "     304      ##STR376##      H " " "     305      ##STR377##      CH.sub.3 CH.sub.3 N NO.sub.2     306      ##STR378##      H " " "     307 " CH.sub.3 " " "     308      ##STR379##      H " " "     309 " CH.sub.3 " " "     310      ##STR380##      H " " "     311 " CH.sub.3 " " "     312      ##STR381##      H " " "     313 " CH.sub.3 " " "     314      ##STR382##      H CH.sub.3 N NO.sub.2     315 " CH.sub.3 " " "     316      ##STR383##      H " " "     317 " CH.sub.3 " " "     318      ##STR384##      H " " "     319 " CH.sub.3 " " "      320 " " C.sub.2      H.sub.5 " "                                              321 " C.sub.2     H.sub.5 CH.sub.3 " "     322      ##STR385##      H " " "     323 " CH.sub.3 " " "     324      ##STR386##      H CH.sub.3 N NO.sub.2     325 " CH.sub.3 " " "     326      ##STR387##      H " " "     327 " CH.sub.3 " " "     328      ##STR388##      H " " "     329 " CH.sub.3 " " "     330      ##STR389##      H " " "     331 " CH.sub.3 " " "     332      ##STR390##      H " " "     333 " CH.sub.3 " " "     334      ##STR391##      H " " "     335 " CH.sub.3 " " "     336      ##STR392##      H H N NO.sub.2     337 " " CH.sub.3 " "      338 " " C.sub.2      H.sub.5 " "                                              339 " "     CH.sub.2      Cl " "                                                           340 "     " CH.sub.2      F " "              341 " "      ##STR393##      " "     342 " " CH.sub.2      SCH.sub.3 " "                                            343 " "     CH.sub.2      OCH.sub.3 " "            344      ##STR394##      CH.sub.3 H N NO.sub.2     345 " " CH.sub.3 " "      346 " " CH.sub.2      Cl " "                                                  347 " "     CH.sub.2      F " "                                                            348 "     " C.sub.2      H.sub.5 " "             349 " "      ##STR395##      " "     350 " " CH.sub.2      SCH.sub.3 " "                                            351 " "     CH.sub.2      OCH.sub.3 " "                                                    352 "     " C.sub.3 H.sub.7      (i) " "                                                 353 " " C.sub.4     H.sub.9      (t) " "           354      ##STR396##      C.sub.2      H.sub.5 H N NO.sub.2            355 " " CH.sub.3 " "      356 " " CH.sub.2      Cl " "                                                  357 " " C.sub.2     H.sub.5 " "      358 " C.sub.3 H.sub.7      (i) H " "                                          359 " " CH.sub.3 " "      360 " " C.sub.2      H.sub.5 " "                                              361 " COCH.sub.     3 H " "      362 " " CH.sub.3 " "      363 " SO.sub.2      CH.sub.3 H " "                                            364 " "     CH.sub.3 " "     365      ##STR397##      H H CH NO.sub.2 [116-118]     366 " " CH.sub.3 " " [133-135]      367 " " CH.sub.2      Cl " "                                                  368 " " C.sub.2     H.sub.5 " " [95-98]      369 " " C.sub.3 H.sub.7      (i) " " [150-152]                                370 " " C.sub.4     H.sub.7      (t) " "                                                           371 "     " CHCH.sub.2       " "                                                         372 " "     CHCHCH.sub.3 " "      373 " " CH.sub.2      CN " "                                                  374 " "     CH.sub.2      NO.sub.2 " "                                                     375 "     " CH.sub.2 COOC.sub.2      H.sub.5 " "                          376      ##STR398##      H      ##STR399##      CH NO.sub.2     377 " "      ##STR400##      " "     378 " "      ##STR401##      " "     379 " "      ##STR402##      " "     380 " CH.sub.3 H " "      381 " " CH.sub.3 " " [79-82]      382 " " CH.sub.2      Cl " "                                                  383 " " C.sub.2     H.sub.5 " " [101-104]      384 " " C.sub.3 H.sub.7      (i) " "                                          385 " " C.sub.4     H.sub.7      (t) " "                                                           386 "     " CHCH.sub.2       " "                                                         387 " "     CHCHCH.sub.3 " "     388      ##STR403##      CH.sub.3 CH.sub.2      CN CH NO.sub.2                       389 " " CH.sub.2      NO.sub.2 " "                           390 " " CH.sub.2 COOC.sub.2     H.sub.5 " "     391 " "      ##STR404##      " "     392 " "      ##STR405##      " "     393 " "      ##STR406##      " "     394 " "      ##STR407##      " "     395 " C.sub.2      H.sub.5 H " "                                               396 " "     CH.sub.3 " "      397 " " C.sub.2      H.sub.5 " "                                              398 " C.sub.3     H.sub.7      (i) H " "                                                         399 "     " CH.sub.3 " "     400      ##STR408##      C.sub.3 H.sub.7 (i) C.sub.2      H.sub.5 CH NO.sub.2                                 401 "      ##STR409##      H " "     402 " " CH.sub.3 " "      403 " " C.sub.2      H.sub.5 " "                                              404 " CH.sub.2     CHCH.sub.2       H " "                                                         405 " "     CH.sub.3 " "      406 " " C.sub.2      H.sub.5 " "                     407 "      ##STR410##      H " "     408 " " CH.sub.3 " "      409 " " C.sub.2      H.sub.5 " "                                              410 " CHO H "     "      411 " " CH.sub.3 " "     412      ##STR411##      CHO C.sub.2      H.sub.5 CH NO.sub.2                 413 " COCH.sub.3 H " "      414 " " CH.sub.3 " "      415 " " C.sub.2      H.sub.5 " "                                              416 " SO.sub.2     CH.sub.3 H " "      417 " " CH.sub.3 " "      418 " " C.sub.2      H.sub.5 " "                                              419 " COOC.sub.     2      H.sub.5 H " "     420 " " CH.sub.3 " "      421 " " C.sub.2      H.sub.5 " "                                              422 " OC.sub.2     H.sub.5 H " "      423 " " CH.sub.3 " "      424 " " C.sub.2      H.sub.5 " "                                              425 " CH.sub.2     CCH H " "      426 " " CH.sub.3 " "      427 " " C.sub.2      H.sub.5 " "                     428      ##STR412##      H CH.sub.3 CH NO.sub.2     429 " CH.sub.3 " " "     430      ##STR413##      H " " "     431 " CH.sub.3 " " "     432      ##STR414##      H " " "     433 " CH.sub.3 " " "     434      ##STR415##      H " " "     435 " CH.sub.3 " " "     436      ##STR416##      H " " "     437 " CH.sub.3 " " "     438      ##STR417##      H " " "     439 " CH.sub.3 " " "     440      ##STR418##      H CH.sub.3 CH NO.sub.2     441 " CH.sub.3 " " "     442      ##STR419##      H " " "     443 " CH.sub.3 " " "     444      ##STR420##      H " " "     445 " CH.sub.3 " " "     446      ##STR421##      H " " "     447 " CH.sub.3 " " "     448      ##STR422##      H " " "     449 " CH.sub.3 " " "     450      ##STR423##      H " " "     451 " CH.sub.3 " " "     452      ##STR424##      H CH.sub.3 CH NO.sub.2     453 " CH.sub.3 " " "     454      ##STR425##      H " " "     455 " CH.sub.3 " " "     456      ##STR426##      H " " "     457 " CH.sub.3 " " "     458      ##STR427##      H " " "     459 " CH.sub.3 " " "     460      ##STR428##      H " " "     461 " CH.sub.3 " " "     462      ##STR429##      H CH.sub.3 CH NO.sub.2     463 " CH.sub.3 " " "     464      ##STR430##      H " " "     465 " CH.sub.3 " " "     466      ##STR431##      H " " "     467 " CH.sub.3 " " "     468      ##STR432##      H " " "     469 " CH.sub.3 " " "     470      ##STR433##      H " " "     471 " CH.sub.3 " " "     472      ##STR434##      H " " "     473      ##STR435##      CH.sub.3 CH.sub.3 CH NO.sub.2     474      ##STR436##      H " " "     475 " CH.sub.3 " " "     476      ##STR437##      H " " "     477 " CH.sub.3 " " "     478      ##STR438##      H " " "     479 " CH.sub.3 " " "     480      ##STR439##      H " " "     481 " CH.sub.3 " " "     482      ##STR440##      H " " "     483 " CH.sub.3 " " "     484      ##STR441##      H CH.sub.3 CH NO.sub.2     485 " CH.sub.3 " " "     486      ##STR442##      H " " "     487 " CH.sub.3 " " "      488 " " C.sub.2      H.sub.5 " "                                              489 " C.sub.2     H.sub.5 CH.sub.3 " "     490      ##STR443##      H " " "     491 " CH.sub.3 " " "     492      ##STR444##      H " " "     493 " CH.sub.3 " " "     494      ##STR445##      H " " "     495 " CH.sub.3 " " "     496      ##STR446##      H CH.sub.3 CH NO.sub.2     497 " CH.sub.3 " " "     498      ##STR447##      H " " "     499 " CH.sub.3 " " "     500      ##STR448##      H " " "     501 " CH.sub.3 " " "     502      ##STR449##      H H CH NO.sub.2     503 " " CH.sub.3 " "      504 " " CH.sub.2      Cl " "                                                  505 " " C.sub.2     H.sub.5 " "      506 " " C.sub.3 H.sub.7      (i) " "                                          507 " " C.sub.4     H.sub.9      (t) " "                                                           508 "     CH.sub.3 H " "      509 " " CH.sub.3 " "      510 " " CH.sub.2      Cl " "                                                  511 " " C.sub.2     H.sub.5 " "     512 " "      ##STR450##      " "     513      ##STR451##      CH.sub.3 C.sub.3 H.sub.7      (i) CH NO.sub.2                              514 " " C.sub.4 H.sub.9      (t) " "                  515 " C.sub.2      H.sub.5 H " "                     516 " " CH.sub.3 " "      517 " " C.sub.2      H.sub.5 " "                     518 "      ##STR452##      H " "     519 " " CH.sub.3 " "      520 " " C.sub.2      H.sub.5 " "                                              521 " COCH.sub.     3 H " "      522 " " CH.sub.3 " "      523 " " C.sub.2      H.sub.5 " "                                              524 " SO.sub.2     CH.sub.3 H " "      525 " " CH.sub.3 " "      526 " " C.sub.2      H.sub.5 " "                     527      ##STR453##      H H CH CN     528 " " CH.sub.3 " " [95-98]      529 " " CH.sub.2      Cl " "                                                  530 " " C.sub.2     H.sub.5 " "      531 " " C.sub.3 H.sub.7      (i) " "                                          532 " " C.sub.4     H.sub.9      (t) " "                                                           533 "     " CHCH.sub.2       " "                                                         534 " "     CHCHCH.sub.3 " "      535 " " CH.sub.2      CN " "                                                  536 " "     CH.sub.2      NO.sub.2 " "                                                     537 "     " CH.sub.2 COOC.sub.2      H.sub.5 " "                          538      ##STR454##      H      ##STR455##      CH CN     539 " "      ##STR456##      " "     540 " "      ##STR457##      " "     541 " "      ##STR458##      " "     542 " CH.sub.3 H " "      543 " " CH.sub.3 " " n.sub.D      .sup.29 1.5941                              544 " " CH.sub.2 Cl " "          545 " " C.sub.2      H.sub.5 " "                                          546 " " C.sub.3     H.sub.7      (i) " "                                                           547 "     " C.sub.4 H.sub.9      (t) " "                                                 548 " "     CHCH.sub.2       " "                                                           549 " "     CHCHCH.sub.3 " "     550      ##STR459##      CH.sub.3 CH.sub.2      CN CH CN                       551 " " CH.sub.2      NO.sub.2 " "                           552 " " CH.sub.2 COOC.sub.2     H.sub.5 " "     553 " "      ##STR460##      " "     554 " "      ##STR461##      " "     555 " "      ##STR462##      " "     556 " "      ##STR463##      " "     557 " C.sub.2      H.sub.5 H " "                                               558 " "     CH.sub.3 " "      559 " " C.sub.2      H.sub.5 " "                                              560 " C.sub.3     H.sub.7      (i) H " "                                                         561 "     " CH.sub.3 " "     562      ##STR464##      C.sub.3 H.sub.7 (i) C.sub.2      H.sub.5 CH CN                                 563 "      ##STR465##      H " "     564 " " CH.sub.3 " "      565 " " C.sub.2      H.sub.5 " "                                              566 " CH.sub.2     CHCH.sub.2       H " "                                                         567 " "     CH.sub.3 " "      568 " " C.sub.2      H.sub.5 " "                     569 "      ##STR466##      H " "     570 " " CH.sub.3 " "      571 " " C.sub.2      H.sub.5 " "                                              572 " CHO H "     "      573 " " CH.sub.3 " "     574      ##STR467##      CHO C.sub.2      H.sub.5 CH CN                 575 " COCH.sub.3 H " "      576 " " CH.sub.3 " "      577 " " C.sub.2      H.sub.5 " "                                              578 " SO.sub.2     CH.sub.3 H " "      579 " " CH.sub.3 " "      580 " " C.sub.2      H.sub.5 " "                                              581 " COOC.sub.     2      H.sub.5 H " "     582 " " CH.sub.3 " "      583 " " C.sub.2      H.sub.5 " "                                              584 " OC.sub.2     H.sub.5 H " "      585 " " CH.sub.3 " "      586 " " C.sub.2      H.sub.5 " "                                              587 " CH.sub.2     CCH H " "      588 " " CH.sub.3 " "      589 " " C.sub.2      H.sub.5 " "                     590      ##STR468##      H CH.sub.3 CH CN     591 " CH.sub.3 " " "     592      ##STR469##      H " " "     593 " CH.sub.3 " " "     594      ##STR470##      H " " "     595 " CH.sub.3 " " "     596      ##STR471##      H " " "     597 " CH.sub.3 " " "     598      ##STR472##      H " " "     599 " CH.sub.3 " " "     600      ##STR473##      H " " "     601 " CH.sub.3 " " "     602      ##STR474##      H CH.sub.3 CH CN     603 " CH.sub.3 " " "     604      ##STR475##      H " " "     605 " CH.sub.3 " " "     606      ##STR476##      H " " "     607 " CH.sub.3 " " "     608      ##STR477##      H " " "     609 " CH.sub.3 " " "     610      ##STR478##      H " " "     611 " CH.sub.3 " " "     612      ##STR479##      H " " "     613 " CH.sub.3 " " "     614      ##STR480##      H CH.sub.3 CH CN     615 " CH.sub.3 " " "     616      ##STR481##      H " " "     617 " CH.sub.3 " " "     618      ##STR482##      H " " "     619 " CH.sub.3 " " "     620      ##STR483##      H " " "     621 " CH.sub.3 " " "     622      ##STR484##      H " " "     623 " CH.sub.3 " " "     624      ##STR485##      H CH.sub.3 CH CN     625 " CH.sub.3 " " "     626      ##STR486##      H " " "     627 " CH.sub.3 " " "     628      ##STR487##      H " " "     629 " CH.sub.3 " " "     630      ##STR488##      H " " "     631 " CH.sub.3 " " "     632      ##STR489##      H " " "     633 " CH.sub.3 " " "     634      ##STR490##      H " " "     635      ##STR491##      CH.sub.3 CH.sub.3 CH CN     636      ##STR492##      H " " "     637 " CH.sub.3 " " "     638      ##STR493##      H " " "     639 " CH.sub.3 " " "     640      ##STR494##      H " " "     641 " CH.sub.3 " " "     642      ##STR495##      H " " "     643 " CH.sub.3 " " "     644      ##STR496##      H CH.sub.3 CH CN     645 " CH.sub.3 " " "     646      ##STR497##      H " " "     647 " CH.sub.3 " " "     648      ##STR498##      H " " "     649 " CH.sub.3 " " "      650 " " C.sub.2      H.sub.5 " "                                              651 " C.sub.2     H.sub.5 CH.sub.3 " "     652      ##STR499##      H CH.sub.3 CH CN     653 " CH.sub.3 " " "     654      ##STR500##      H " " "     655 " CH.sub.3 " " "     656      ##STR501##      H " " "     657 " CH.sub.3 " " "     658      ##STR502##      H " " "     659 " CH.sub.3 " " "     660      ##STR503##      H " " "     661 " CH.sub.3 " " "     662      ##STR504##      H " " "     663 " CH.sub.3 " " "     664      ##STR505##      H H CH CN     665 " " CH.sub.3 " "      666 " " CH.sub.2      Cl " "                                                  667 " " C.sub.2     H.sub.5 " "      668 " " C.sub.3 H.sub.7      (i) " "                                          669 " " C.sub.4     H.sub.9      (t) " "                                                           670 "     CH.sub.3 H " "      671 " " CH.sub.3 " "      672 " " CH.sub.2      Cl " "                                                  673 " " C.sub.2     H.sub.5 " "     674 " "      ##STR506##      " "     675      ##STR507##      CH.sub.3 C.sub.3 H.sub.7      (i) CH CN                              676 " " C.sub.4 H.sub.9      (t) " "                  677 " C.sub.2      H.sub.5 H " "                     678 " " CH.sub.3 " "      679 " " C.sub.2      H.sub.5 " "                     680 "      ##STR508##      H " "     681 " " CH.sub.3 " "      682 " " C.sub.2      H.sub.5 " "                                              683 " COCH.sub.     3 H " "      684 " " CH.sub.3 " "      685 " " C.sub.2      H.sub.5 " "                                              686 " SO.sub.2     CH.sub.3 H " "     687      ##STR509##      SO.sub.2      CH.sub.3 CH.sub.3 CH CN             688 " " C.sub.2      H.sub.5 " "     *1 .sup.1 HNMR(CDCl.sub.3) δ; ppm 3.32 (s, 3H), 4.63 (s, 2H), 7.37     (d, 1H), 7.62 (dd, 1H), 8.37 (d, 1H)

The compounds of this invention exhibit high insecticidal activitiesagainst various species of insect pests such as cutworms, diamondbackmoth, aphids, leafhoppers and planthoppers. In recent years the decreaseof the control effects of organophosphorus and carbamate insecticides,which is caused by the development of resistance to these insecticides,has become serious problem. In such situations, the development of newinsecticides which is effective on the resistant pests has been desired.The compounds of this invention possess superior insecticidal activitiesagainst not only susceptible strains but also resistant ones.

The insecticides covered by this invention contain as active ingredientsone or more types of the compounds as expressed by the general formula(1). These active ingredients, may be used as-produced but normally theyare used in any of the forms which ordinary agricultural chemicals cantake, namely wettable powder, dust, emulsifiable concentrate, suspensionconcentrates, smoking chemicals, fumigant, granule, or otherformulations. For additives and carriers are used soybean flour, wheatflour or other vegetable flours, diatomaceous earth, apatite, gypsum,talc, pyrophyllite, clay or other fine mineral powders, when solidformulations are intended.

When liquid formulations are intended, then for solvents are usedkerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane,cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone,water, etc. A surface active agent may, if necessary, be added in orderto give a homogeneous and suitable formulation. The wettable powders,emulsifiable concentrates, suspension thus obtained are diluted withwater concentrates, etc. into suspensions or emulsions of a prescribedconcentration, before they are actually sprayed on plants in the field.In the case of dusts or granules, they are directly applied withoutfurther processing.

It goes without saying that the compound(s) of this invention iseffective even alone, but it can be used by mixing with various types ofinsecticides, acaricides and fungicides.

Typical examples of acaricides and insecticides which can be used bymixing with the compounds of this invention are described below:

Acaricides (fungicides):

chlorobenzilate, chloropropylate, proclonol, bromopropylate, dicofol,dinobuton, binapacryl, chlordimeform, amitraz, propargite, PPPS,benzoximate, hexythiazox, fenbutatin oxide, polynactine, chinomethionat,thioquinox, chlorfenson, tetradifon, phenproxide, avermectins,clofentezine, flubenzimine, fenazaquin, pyridaben, fenproximate,chlorfenethol, thiophanate-methyl, benomyl, thiram, iprobenfos,edifenfos, fthalide, probenazole, isoprothiolane, chorothalonil, captan,polyoxin-B, blasticidin-S, kasugamycin, validamycin, tricyclazole,pyroquilon, phenazine oxide, mepronil, flutolanil, pencycuron,iprodione, hymexazole, metalaxyl, triflumizole, diclomezine,tecloftalam, vinclozolin, procymidone, bitertanol, triadimefon,prochloraz, pyrifenox, fenarimal, fenpropimorph, triforine, metalaxyl,oxycarboxin, pefrazoate, diclomedine, fluazinam, oxadixyl, ethoquinolac,TPTH, propamocarb, fosetyl, dihydrostreptomycin, anilazine, dithianon,diethofencarb. Organophosphorus-type and carbamate-type insecticides(acaridides): fenthion, fenitrothion, diazinon, chlorpyrifos,oxydeprofos, vamidothion, phenthoate, dimethoate, formothion, malathion,trichlorfon, thiometon, phosmet, menazon, dichlorvos, acephate, EPBP,dialifos, parathion-methyl, oxydemeton-methyl, ethion, aldicarb,propoxur, methomyl, fenobucarb, BPMC, pyraclofos, monocrotophos,salithion, cartap, carbosulfan, carbofuran, benfuracarb, metolcarb,carbaryl, pirimicarb, ethiofencarb, fenoxycarb,

Pyrethroide-type insecticides (acaricides): permethrin, cypermethrin,deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin,tetramethrin, resmethrin, parthrin, dimethrin, proparthrin, bifenthrin,prothrin, fluvalinate, cyhalothrin, cyhalothrin, flucythrinate,ethofenprox, cycloprothrin, tralomethrin, silaneophan.

Benzoylphenylurea-type and other types insecticides:

diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin,pyriproxyfen, flufenoxuron, Machine oil.

Same examples of the formulations are given below. The carriers,surface-active agents, etc. that are added, however, are not limited tothese Examples.

Example 7

Emulsifiable concentrate

    ______________________________________                                        The compound of this invention                                                                     10 parts                                                 Alkylphenyl polyoxyethylene                                                                         5 parts                                                 Dimethyl formamide   50 parts                                                 Xylene               35 parts                                                 ______________________________________                                    

These components are mixed and dissolved and, for use in spraying, theliquid mixture is water-diluted into an emulsion.

Example 8

Wettable powder

    ______________________________________                                        The compound of this invention                                                                     20 parts                                                 Higher alcohol sulfuric ester                                                                       5 parts                                                 Diatomaceous earth   70 parts                                                 Silica                5 parts                                                 ______________________________________                                    

These components are mixed and ground to fine powder, which for use inspraying, are water-diluted into a suspension.

Example 9

Dust

    ______________________________________                                        The compound of this invention                                                                       5 parts                                                Talc                 94.7 parts                                               Silica                0.3 parts                                               ______________________________________                                    

These are mixed and ground and used as-ground in spraying.

Example 10

Granule

    ______________________________________                                        The compound of this invention                                                                          5 parts                                             Clay                     73 parts                                             Bentonite                20 parats                                            Sodium dioctylsulfosuccinate                                                                            1 part                                              Sodium phosphate          1 part                                              ______________________________________                                    

The above compounds are granulated, and applied as it is when used.

Industrial applicability:

The tests below show the insecticidal activity of the compounds of thisinvention.

Test 1 Efficacy for cotton aphid

30 to 50 insects of cotton aphid per plot were inoculated using a smallbrush on cucumber leaves which were seeded in pots, 10 cm in diameter,and 10 days old after germination. A day later, wounded insect pestswere removed, and a chemical solution, which was prepared in the waythat the emulsifiable concentrate described in Example 7 of the aboveexample of insecticide was diluted with water to 125 ppm of compoundconcentration according to the prescription, was sprayed. The pots wereplaced in a thermostatic room at temperature of 25 ° C. and humidity of65%. The number of survival pests was counted 7 days later and thecontrol efficacy was calculated by comparing with that of untreatedplot. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                       Control Efficacy (7 days later)                                Compound No.   125 ppm                                                        ______________________________________                                         1              100%                                                           2             100                                                             3             100                                                             4             100                                                             6             100                                                             8             100                                                            10             100                                                            16             100                                                            20             100                                                            21             100                                                            22             100                                                            23             100                                                            24             100                                                            25             100                                                            27             100                                                            29             100                                                            31             100                                                            32             100                                                            33             100                                                            38             100                                                            44             100                                                            48             100                                                            50             100                                                            51             100                                                            53             100                                                            57             100                                                            60             100                                                            62             100                                                            64             100                                                            66             100                                                            68             100                                                            70             100                                                            72             100                                                            73             100                                                            74             100                                                            78             100                                                            80             100                                                            82             100                                                            84             100                                                            86             100                                                            88             100                                                            92             100                                                            96             100                                                            100            100                                                            102            100                                                            115            100                                                            116            100                                                            120            100                                                            124            100                                                            130            100                                                            132            100                                                            136            100                                                            144            100                                                            145            100                                                            146            100                                                            148            100                                                            149            100                                                            150            100                                                            151            100                                                            152            100                                                            163            100                                                            164            100                                                            169            100                                                            170            100                                                            171            100                                                            172            100                                                            173            100                                                            174            100                                                            177            100                                                            178            100                                                            188            100                                                            189            100                                                            190            100                                                            194            100                                                            203            100                                                            206            100                                                            213            100                                                            236            100                                                            366            100                                                            368            100                                                            381            100                                                            383            100                                                            543            100                                                            Comparative compound A                                                                        27                                                            Comparative compound B                                                                       100                                                            ______________________________________                                        Comparative compound A:                                                        -                                                                             ##STR510##                                                                   Comparative compound B:                                                        ##STR511##                                                                     Test 2 Efficacy for green rice leafhopper

Rice seedlings of 7 days old after germination were immersed in achemical solution, which was prepared in the way that the emulsifiableconcentrate described in Example 7 of the above example of insecticidewas diluted with water to 125 ppm of compound concentration according toprescription, for 30 seconds. After dried in air, the treated seedlingswere placed in test tubes and 10 insects of 3rd-instar larvae of greenrice leafhopper resistant to the organophosphorus and carbamateinsecticides were inoculated. The tubes were covered with gauze, andplaced in a thermostatic room at temperature of 25° C. and humidity of65%. The mortality was checked 5 days later. The results are shown inTable 3.

                  TABLE 3                                                         ______________________________________                                                         % mortality (5 days later)                                   Compound No.     125 ppm                                                      ______________________________________                                         1                100%                                                         2               100                                                           4               100                                                           6               100                                                           8               100                                                          10               100                                                          16               100                                                          18               100                                                          20               100                                                          21               100                                                          22               100                                                          23               100                                                          24               100                                                          25               100                                                          27               100                                                          28               100                                                          29               100                                                          31               100                                                          32               100                                                          33               100                                                          35               100                                                          36               100                                                          44               100                                                          48               100                                                          50               100                                                          51               100                                                          53               100                                                          57               100                                                          60               100                                                          62               100                                                          66               100                                                          68               100                                                          72               100                                                          73               100                                                          74               100                                                          78               100                                                          82               100                                                          84               100                                                          86               100                                                          88               100                                                          92               100                                                          96               100                                                          100              100                                                          102              100                                                          116              100                                                          120              100                                                          124              100                                                          130              100                                                          132              100                                                          136              100                                                          144              100                                                          146              100                                                          148              100                                                          150              100                                                          152              100                                                          164              100                                                          169              100                                                          170              100                                                          171              100                                                          172              100                                                          173              100                                                          174              100                                                          178              100                                                          188              100                                                          190              100                                                          201              100                                                          203              100                                                          213              100                                                          236              100                                                          366              100                                                          368              100                                                          369              100                                                          381              100                                                          Comparative Compound A                                                                          0                                                           Comparative Compound B                                                                          0                                                           Comparative Compound C                                                                          0                                                           ______________________________________                                        Comparative compound A and B: The same as test 1                              Compound C:                                                                    ##STR512##                                                                     Test 3 Efficacy for rice armyworm

The test compounds were formulated into the wettable powder in the samemanner as Example 8. The compounds were diluted with water to 125 ppm. Amaize leaf was immersed in the chemical solution for 30 seconds. Afterair-dried, the treated leaf was placed in a petri dish and five3rd-instar larvae of rice armyworm were inoculated. The petri disheswere covered with glass lids, and placed in a thermostatic room at 25°C. and 65% relative humidity. The mortality was checked 5 days later.Two replications were conducted in the each test. The results are shownin Table 4.

                  TABLE 4                                                         ______________________________________                                                         % mortality (5 days later)                                   Compound No.     125 ppm                                                      ______________________________________                                        21                100%                                                        22               100                                                          23               100                                                          24               100                                                          25               100                                                          51               100                                                          57               100                                                          88               100                                                          92               100                                                          148              100                                                          172              100                                                          381              100                                                          Comparative compound A                                                                          0                                                           Comparative compound B                                                                          0                                                           Comparative compound D                                                                          40                                                          ______________________________________                                        Comparative compound A and B: The same as Test 1                              Compound D:                                                                    ##STR513##                                                               

We claim:
 1. An insecticidal compound of the formula ##STR514## whereinA completes a 6 membered aromatic ring having one heteroatomic ringmember comprising nitrogen, provided, however, that the ring is notunsubstituted 2-pyridyl;R₁ is hydrogen or C₁₋₅ alkyl, C₁₋₅ haloalkyl,C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano, halogen,phenoxy, or C₁₋₅ dialkylamino; X is C₁₋₃ alkylene or C₁₋₃ alkylidene; R₂is hydrogen, carbamoyl, monoalkylcarbomoyl, C₁₋₅ dialkylcarbamoyl,thiocarbamoyl, monoalkylthiocarbamoyl, sulfamoyl, monoalkylsulfamoyl,C₁₋₅ dialkylsulfamoyl, C₁₋₅ alkyl, C₁₋₅ alkyl substituted with halogen,C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkoxycarbonyl, cyano, aryl, haloaryl,C₁₋₅ alkoxyaryl, furyl, thienyl, pyridyl, halopyridyl, thiazolyl orhalothiazolyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₈ cycloalkyl, C₃₋₈cycloalkenyl, aryl, or the radical

    --Y--R.sub.5

whereinY is O, S(O)_(n), CO, CS or CO₂ ; n is O, 1 or 2, R₅ is hydrogen,C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₈ cycloalkyl, C₃₋₅cycloalkenyl, aryl or haloaryl; R₃ is hydrogen, C₁₋₅ alkyl, C₁₋₅ alkylsubstituted with halogen, C₁₋₅ alkoxy, C₁₋₅ alylthio, C₁₋₅alkoxycarbonyl, cyano, aryl, haloaryl, amino, monoalkylamino, C₁₋₅dialkylamino, cyanoimino, N-halopyridyl-C₁₋₅ alkylamino,N-(halopyridyl-C₁₋₅ alkyl)-C₁₋₅ alkylamino, C₂₋₅ alkenyl, C₂₋₅ alkynyl,C₃₋₈ cycloalkyl, or C₃₋₅ cycloalkenyl; R₄ is cyano or nitro; Z is CH orN;with the proviso that the insecticidal compound of such formula cannot be a compound wherein; R₁ is hydrogen or C₁₋₅ alkyl, C₁₋₅ haloalkyl,C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano, halogen, or C₁₋₅dialkylamino; X is C₁₋₃ alkylene or C₁₋₃ alkylidene; R₂ is hydrogen,carbamoyl, monoalkylcarbamoyl, C₁₋₅ dialkylcarbamoyl, thiocarbamoyl,monoalkylthiocarbamoyl, sulfamoyl, monoalkylsulfamoyl, C₁₋₅dialkylsulfamoyl, C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₈cycloalkyl, C₃₋₅ cycloalkenyl, aryl, or the radical

    --Y--R.sub.5

whereinY is O, S(O)n, CO, CS or CO₂, n is O, 1 or 2, R₅ is hydrogen,C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₅ cycloalkyl, C₃₋₅cycloalkenyl, or aryl; R₃ is hydrogen, C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅alkynyl, C₃₋₈ cycloalkyl, or C₃₋₈ cycloalkenyl; R₄ is cyano or nitro; Zis CH or N; and an insecticidal acceptable salt thereof.
 2. Aninsecticidal compound according to claim 1 whereinR₂ is hydrogen,monoalkylcarbamoyl, C₁₋₅ dialkylcarbamoyl, C₁₋₅ alkyl, C₁₋₅ alkylsubstituted with halogen, C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅alkoxycarbonyl, cyano, aryl, haloaryl, C₁₋₅ alkoxyaryl, furyl, thienyl,pyridyl, halopyridyl, thiazolyl, halothiazolyl, C₂₋₅ alkenyl, C₂₋₅alkynyl, C₃₋₈ cycloalkyl, aryl, or the radical

    --Y--R.sub.5

whereinis O, CO, CO₂, or SO₂ ; R₂ is C₁₋₅ alkyl, aryl or haloaryl; R₃ ishydrogen, C₁₋₅ alkyl, C₁₋₅ alkyl substituted with halogen, C₁₋₅ alkoxy,C₁₋₅ alkylthio, C₁₋₅ alkoxycarbonyl, cyano, aryl, haloaryl, amino,monoalkylamino, C₁₋₅ dialkylamino, cyanoimino, N-halopyridyl-C₁₋₅alkylamino, N-(halopyridyl-C₁₋₅ alkyl)-C₁₋₅ alkylamino, or C₃₋₈cycloalkyl; Z is CH or N;and an insecticidal acceptable salt thereof. 3.An insecticidal compound according to claim 2 wherein Z is N.
 4. Apyridine compound of the formula ##STR515## wherein R₁ representshydrogen, C₁₋₅ alkyl, C₁₋₅ haloalkyl, C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅alkylsulfonyl, cyano, halogen, phenoxy or C₁₋₅ dialkylamino;X representsan optionally substituted C₁₋₃ alkylene or C₁₋₃ alkylidene; R₂represents hydrogen, carbamoyl, monoalkylcarbamoyl, C₁₋₅dialkylcarbamoyl, thiocarbamoyl, monoalkylthiocarbamoyl, sulfamoyl,monoalkylsulfamoyl, C₁₋₅ dialkylsulfamoyl, C₁₋₅ alkyl, C₂₋₅ alkenyl,C₂₋₅ alkynyl, C₃₋₈ cycloalkyl, C₃₋₈ cycloalkenyl, aryl, or the radical

    --Y--R.sub.5

whereinY represents O, CO, CO₂ or SO₂ ; R₅ represents C₁₋₅ alkyl, aryl,or haloaryl; R₃ represents hydrogen, C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅alkenyl, C₃₋₈ cycloalkyl or C₃₋₈ cycloalkenyl; R₄ represents a cyano ora nitro; Z represents CH or N;and an insecticidal acceptable saltthereof.
 5. A pyridine compound according to claim 4 wherein Z is N. 6.An insecticidal compound of the formula ##STR516## wherein A completes a6-membered aromatic ring selected from the group pyridyl, whereinpyridyl is substituted with C₁₋₅ alkyl, C₁₋₅ haloalkyl, C₁₋₅ alkoxy,C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano, halogen, phenoxy or C₁₋₅dialkylamino, pyrazinyl, pyrazinyl substituted with halogen or thiazolylsubstituted with halogen or C₁₋₅ alkyl;R₁ is hydrogen or C₁₋₅ alkyl,C₁₋₅ haloalkyl, C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano,halogen, phenoxy, or C₁₋₅ dialkylamino; X is C₁₋₃ alkylene or C₁₋₃alkylidene; R₂ is C₁₋₅ alkyl substituted with halogen, C₁₋₅ alkoxy, C₁₋₅alkylthio, C₁₋₅ alkoxycarbonyl, cyano, aryl, haloaryl, C₁₋₅ alkoxyaryl,furyl, thienyl, pyridyl, halopyridyl, thiazolyl or halothiazolyl; R₃ isC₁₋₅ alkyl substituted with halogen, C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅alkoxycarbonyl, cyano, aryl, haloaryl, amino, monoalkylamino, C₁₋₅dialkylamino, cyanomino, N-halopyridyl-C₁₋₅ alkylamino orN-(halopyridyl-C₁₋₅ alkyl)-C₁₋₅ alkylamino; R₄ is cyano or nitro; Z isCH or N;and an insecticidal acceptable salt thereof.
 7. An insecticidalcompound according to claim 6 wherein Z is N.